High mobility periodic structured organic films

ABSTRACT

An high mobility structured organic film comprising a plurality of segments and a plurality of linkers arranged as a covalent organic framework, wherein the structured organic film may be a multi-segment thick structured organic film.

CROSS-REFERENCE TO RELATED APPLICATIONS

This nonprovisional application is related to U.S. patent applicationSer. Nos. 12/716,524; 12/716,449; 12/716,706; 12/716,324; 12/716,686;12/716,571; 12/815,688; 12/845,053; 12/845,235; 12/854,962; 12/854,957;and 12/845,052 entitled “Structured Organic Films,” “Structured OrganicFilms Having an Added Functionality,” “Mixed Solvent Process forPreparing Structured Organic Films,” “Composite Structured OrganicFilms,” “Process For Preparing Structured Organic Films (SOFs) Via aPre-SOF,” “Electronic Devices Comprising Structured Organic Films,”“Periodic Structured. Organic Films,” “Capped Structured Organic FilmCompositions,” “Imaging Members Comprising Capped Structured OrganicFilms. Compositions,” “Imaging Members for Ink-Based Digital PrintingComprising Structured Organic Films,” “Imaging Devices ComprisingStructured Organic Films,” and “Imaging Members Comprising StructuredOrganic Films,” respectively; and U.S. Provisional Application No.61/157,411, entitled “Structured Organic Films” filed Mar. 4, 2009, thedisclosures of which are totally incorporated herein by reference intheir entireties.

BACKGROUND OF THE INVENTION

Materials whose chemical structures are comprised of molecules linked bycovalent bonds into extended structures may be placed into two classes:(1) polymers and cross-linked polymers, and (2) covalent organicframeworks (also known as covalently linked organic networks).

The first class, polymers and cross-linked polymers, is typicallyembodied by polymerization of molecular monomers to form long linearchains of covalently-bonded molecules. Polymer chemistry processes canallow for polymerized chains to, in turn, or concomitantly, become‘cross-linked.’ The nature of polymer chemistry offers poor control overthe molecular-level structure of the formed material, i.e. theorganization of polymer chains and the patterning of molecular monomersbetween chains is mostly random. Nearly all polymers are amorphous, savefor some linear polymers that efficiently pack as ordered rods. Somepolymer materials, notably block co-polymers, can possess regions oforder within their bulk. In the two preceding cases the patterning ofpolymer chains is not by design, any ordering at the molecular-level isa consequence of the natural intermolecular packing tendencies.

The second class, covalent organic frameworks (COFs), differ from thefirst class (polymers/cross-linked polymers) in that COFs are intendedto be highly patterned. In COF chemistry molecular components are calledmolecular building blocks rather than monomers. During COF synthesismolecular building blocks react to form two- or three-dimensionalnetworks. Consequently, molecular building blocks are patternedthroughout COF materials and molecular building blocks are linked toeach other through strong covalent bonds.

COFs developed thus far are typically powders with high porosity and arematerials with exceptionally low density. COFs can store near-recordamounts of argon and nitrogen. While these conventional COFs are useful,there is a need, addressed by embodiments of the present invention, fornew materials that offer advantages over conventional COFs in terms ofenhanced characteristics.

However, the above mentioned polymers, cross-linked polymers, andcovalent organic frameworks lack the intrinsic high (electron/hole)mobilities necessary for attaining breakthrough performance in organicelectronics. The requisite high mobilities may be achieved by the SOFsof the present disclosure, which have a high degree of long-rangemolecular-level order (periodic). The high mobility materials of thepresent disclosure are networked (linked by strong bonds) into periodicstructures of provides an opportunity to combine high electricalperformance with the inherent chemical and mechanical robustnessaccessed by networked materials.

SUMMARY OF THE DISCLOSURE

There is provided in embodiments a high mobility ordered (periodic)structured organic film comprising a plurality of segments and aplurality of linkers arranged as a covalent organic framework, whereinat a macroscopic level the covalent organic framework is a film. SuchSOFs may possess long-range molecular order (periodic) and consequentexceptional (hole/electron) mobilities. The present disclosure alsodiscloses methods for producing SOFs possessing high mobility byselecting and using designer molecular building blocks and usingreaction conditions that promote the ordering of building blocks. Highmobility SOFs may be robust films that can be integrated into organicelectronic devices (photoreceptor, TFT, solar cell, etc.) and providebreakthrough electrical and lifetime performance.

BRIEF DESCRIPTION OF THE DRAWINGS

Other aspects of the present disclosure will become apparent as thefollowing description proceeds and upon reference to the followingfigures which represent illustrative embodiments:

FIGS. 1A-O are illustrations of exemplary building blocks whosesymmetrical elements are outlined.

FIG. 2 is an illustration of triangular and linear molecular buildingblocks used to make an imine-linked hexagonal SOF.

FIG. 3 is an illustration of a molecular-level structure of an imine SOFshowing stacking between layers of connected triangular and linearbuilding blocks.

FIG. 4 is a graphic representation of an X-ray diffraction patternpredicted from modeling the SOF structure of the Example.

FIG. 5 is a graphic representation of a density of states diagramillustrating the position of the Fermi level within a band thatindicates the propensity of this SOF to be an electron conductor.

DETAILED DESCRIPTION

In this specification and the claims that follow, singular forms such as“a,” “an,” and “the” include plural forms unless the content clearlydictates otherwise.

The term “SOF” generally refers to a covalent organic framework (COF)that is a film at a macroscopic level. The phrase “macroscopic level”refers, for example, to the naked eye view of the present SOFs.Although. COFs are a network at the “microscopic level” or “molecularlevel” (requiring use of powerful magnifying equipment or as assessedusing scattering methods), the present SOF is fundamentally different atthe “macroscopic level” because the film is for instance orders ofmagnitude larger in coverage than a microscopic level COF network. SOFsdescribed herein that may be used in the embodiments described hereinare high mobility SOFs and have macroscopic morphologies much differentthan typical COFs previously synthesized.

For robust networked organic materials, high mobility is difficult toachieve. The term “high mobility SOF” refers, for example, to a SOFpossessing long-range molecular order (periodic) and consequentexceptional (hole/electron) mobilities, which possess mobilitysubstantially equal to or greater than the mobility of known nominalorganic electronic materials. In the present disclosure, a “highmobility” SOF may have a mobility of greater than about 0.1 cm²/Vs, suchas a mobility ranging from about 0.1 to about 3.0 cm²/Vs, or from about0.2 to about 2 cm²/Vs, or from about 0.5 to about 1.5 cm²/Vs. It isknown that high charge mobility relates to electronic structure of thematerial at the atomic level. Such electronic structure may be referredto as ‘band structure,’ which is an established representation ofelectronic energy levels within a material. Materials that areidentified as comprising a Fermi Level that lies within a band possess aunique ability to transport charge.

In embodiments, the SOF may be a composite SOF. In such an SOF, aportion or region of the SOF may be a composite SOF, while a differentportion or region of the SOF, which may or may not be adjacent to thecomposite SOF, is another type of SOF, such as a periodic SOF. Suchcomposite SOF compositions may alter the properties of SOFs withoutchanging constituent building blocks. For example, the mechanical andphysical properties of the SOF. Optionally, a capping unit may beintroduced into a portion or region of the SOF that is not periodic, sothat the SOF framework is locally ‘interrupted’ where the capping unitsare present.

The SOFs, such as periodic SOFs (which may or may not comprise acomposite and/or capped SOF portion or region), of the presentdisclosure may be at the macroscopic level substantially pinhole-freeSOFs or pinhole-free SOFs having continuous covalent organic frameworksthat can extend over larger length scales such as for instance muchgreater than a millimeter to lengths such as a meter and, in theory, asmuch as hundreds of meters. It will also be appreciated that SOFs tendto have large aspect ratios where typically two dimensions of a SOF willbe much larger than the third. SOFs have markedly fewer macroscopicedges and disconnected external surfaces than a collection of COFparticles.

Additionally, when a capping unit is introduced into a portion or regionof the SOF that is not periodic, the SOF framework is locally‘interrupted’ where the capping units are present. These SOFcompositions are ‘covalently doped’ because a foreign molecule is bondedto the SOF framework when capping units are present. Capped SOFcompositions may alter the properties of SOFs without changingconstituent building blocks. For example, the mechanical and physicalproperties of the portion of the SOF that comprises a capped SOF (wherethe SOF framework is interrupted) may differ from a portion or region ofthe same SOF that is an uncapped SOF, such as a portion or region of theSOF that is periodic.

The SOFs of the present disclosure may be, at the macroscopic level,substantially pinhole-free SOFs or pinhole-free SOFs having continuouscovalent organic frameworks that can extend over larger length scalessuch as for instance much greater than a millimeter to lengths such as ameter and, in theory, as much as hundreds of meters. It will also beappreciated that SOFs tend to have large aspect ratios where typicallytwo dimensions of a SOF will be much larger than the third. SOFs havemarkedly fewer macroscopic edges and disconnected external surfaces thana collection of COF particles.

In embodiments, a “substantially pinhole-free SOF” or “pinhole-free SOF”may be formed from a reaction mixture deposited on the surface of anunderlying substrate. The term “substantially pinhole-free SOF” refers,for example, to an SOF that may or may not be removed from theunderlying substrate on which it was formed and contains substantiallyno pinholes, pores or gaps greater than the distance between the coresof two adjacent segments per square cm; such as, for example, less than10 pinholes, pores or gaps greater than about 250 nanometers in diameterper cm², or less than 5 pinholes, pores or gaps greater than about 100nanometers in diameter per cm². The term “pinhole-free SOF” refers, forexample, to an SOF that may or may not be removed from the underlyingsubstrate on which it was formed and contains no pinholes, pores or gapsgreater than the distance between the cores of two adjacent segments permicron², such as no pinholes, pores or gaps greater than about 500Angstroms in diameter per micron², or no pinholes, pores or gaps greaterthan about 250 Angstroms in diameter per micron², or no pinholes, poresor gaps greater than about 100 Angstroms in diameter per micron².

Molecular Building Block

The SOFs of the present disclosure comprise molecular building blockshaving a segment (S) and functional groups (Fg). Molecular buildingblocks require at least two functional groups (x≧2) and may comprise asingle type or two or more types of functional groups. Functional groupsare the reactive chemical moieties of molecular building blocks thatparticipate in a chemical reaction to link together segments during theSOF forming process. A segment is the portion of the molecular buildingblock that supports functional groups and comprises all atoms that arenot associated with functional groups. Further, the composition of amolecular building block segment remains unchanged after SOF formation.

Functional Group

Functional groups are the reactive chemical moieties of molecularbuilding blocks that participate in a chemical reaction to link togethersegments during the SOF forming process. Functional groups may becomposed of a single atom, or functional groups may be composed of morethan one atom. The atomic compositions of functional groups are thosecompositions normally associated with reactive moieties in chemicalcompounds. Non-limiting examples of functional groups include halogens,alcohols, ethers, ketones, carboxylic acids, esters, carbonates, amines,amides, imines, ureas, aldehydes, isocyanates, tosylates, alkenes,alkynes and the like.

Molecular building blocks contain a plurality of chemical moieties, butonly a subset of these chemical moieties are intended to be functionalgroups during the SOF forming process. Whether or not a chemical moietyis considered a functional group depends on the reaction conditionsselected for the SOF forming process. Functional groups (Fg) denote achemical moiety that is a reactive moiety, that is, a functional groupduring the SOF forming process.

In the SOF forming process the composition of a functional group will bealtered through the loss of atoms, the gain of atoms, or both the lossand the gain of atoms; or, the functional group may be lost altogether.In the SOF, atoms previously associated with functional groups becomeassociated with linker groups, which are the chemical moieties that jointogether segments. Functional groups have characteristic chemistries andthose of ordinary skill in the art can generally recognize in thepresent molecular building blocks the atom(s) that constitute functionalgroup(s). It should be noted that an atom or grouping of atoms that areidentified as part of the molecular building block functional group maybe preserved in the linker group of the SOF.

Capping Unit

Capping units of the present disclosure are molecules that ‘interrupt’the regular network of covalently bonded building blocks normallypresent in an SOF. The capped regions of the SOF compositions of thepresent disclosure are tunable in that the properties of the cappedregions may be varied through the type and amount of capping unitintroduced into the region of the SOF that is not periodic. Cappingunits may comprise a single type or two or more types of functionalgroups and/or chemical moieties.

Segment

A segment is the portion of the molecular building block that supportsfunctional groups and comprises all atoms that are not associated withfunctional groups. Further, the composition of a molecular buildingblock segment remains unchanged after SOF formation. In embodiments, theSOF may contain a first segment having a structure the same as ordifferent from a second segment. In other embodiments, the structures ofthe first and/or second segments may be the same as or different from athird segment, forth segment, fifth segment, etc. A segment is also theportion of the molecular building block that can provide an inclinedproperty. Inclined properties are described later in the embodiments.

A description of various exemplary molecular building blocks, linkers,SOF types, strategies to synthesize a specific SOF type with exemplarychemical structures, building blocks whose symmetrical elements areoutlined, and classes of exemplary molecular entities and examples ofmembers of each class that may serve as molecular building blocks forSOFs are detailed in U.S. patent application Ser. Nos. 12/716,524;12/716,449; 12/716,706; 12/716,324; 12/716,686; 12/716,571; 12/815,688;12/845,053; 12/845,235; 12/854,962; 12/854,957; and 12/845,052 entitled“Structured Organic Films,” “Structured Organic Films Having an AddedFunctionality,” “Mixed Solvent Process for Preparing Structured OrganicFilms,” “Composite Structured Organic Films,” “Process For PreparingStructured Organic Films (SOFs) Via a Pre-SOF,” “Electronic DevicesComprising Structured Organic Films,” “Periodic Structured OrganicFilms,” “Capped Structured Organic Film Compositions,” “Imaging MembersComprising Capped Structured Organic Film Compositions,” “ImagingMembers for Ink-Based Digital Printing Comprising Structured OrganicFilms,” “Imaging Devices Comprising Structured Organic Films,” and“Imaging Members Comprising Structured Organic Films,” respectively; andU.S. Provisional Application No. 61/157,411, entitled “StructuredOrganic Films” filed Mar. 4, 2009, the disclosures of which are totallyincorporated herein by reference in their entireties.

In embodiments, a computer simulation or materials modeling of a SOFcomposition may be used to select a desired structure of an SOF withdesired or predetermined properties. For example, a computer simulationor materials modeling of a specific SOF composition may be used toselect a desired SOF that should conduct electrons. Other non-limitingexamples of properties that can be extracted from computer simulationare optical properties, mechanical properties, atomic-level structuralparameters, diffusion properties, and porous properties. In embodiments,a metric of the computer simulation or materials modeling may be used toselect a specific SOF composition with desired properties. Inembodiments, a metric of the computer simulation may include parameterssuch as, for example, the degree of expected molecular orbital overlap,expected extent of uniformity regarding the spacial orientation of thebuilding blocks, the band structure, atomic-level stresses, geometryoptimization, and X-ray (or other) scattering patterns, among others.

The modeling of SOF structures is facilitated by the modular nature(i.e. reticular chemistry) of their composition. In the art of reticularchemistry, molecular building blocks may be regarded as geometric shapesand consequently the assembly of these ‘molecular shapes’ falls into anumber of predetermined arrangements following reaction of molecularbuilding blocks (the SOF forming reaction). A number of parameters maybe computed and subsequently examined during and following computersimulation of SOF structures to assess properties of a particular SOFstructure.

Exemplary methods to extract properties from computer simulated SOFstructures may include, for example, calculating the band structure ofthe SOF. In embodiments, such a calculation may be employed such thatoptical and electrical properties may be predicted by noting theposition of the Fermi level and the magnitude and position of the bandgap.

In embodiments, methods to extract properties from computer simulated.SOF structures may include information and/or parameters regardingmechanical properties, which may, for example, be estimated bymonitoring the atomic-level stresses on the SOF under sheer. Inembodiments, methods to extract properties from computer simulated SOFstructures may include information and/or parameters regardingstructural metrics, which may, for example, be computed at the atomiclevel following geometry optimization calculations. In embodiments,methods to extract properties from computer simulated SOF structures mayinclude information and/or parameters regarding bulk structuralfeatures, which may, for example, be simulated by calculating the X-ray(or other) scattering pattern of the material. In embodiments, methodsto extract properties from computer simulated SOF structures may includeinformation and/or parameters regarding diffusion properties, which may,for example, be assessed using molecular dynamics methods andsubsequently calculating the population gradient across the SOFstructure. In embodiments, porosity (surface area) may be assessed usingthe Connoly method.

In embodiments, a computer simulation or materials modeling of aspecific SOF composition may be used to select specific molecularbuilding blocks, linkers and SOF type such that the spacial orientationbetween linked molecular building blocks is uniform. In embodiments,reaction components (such as molecular building blocks, etc.,)identified by the computer simulation or materials modeling are used toproduce a SOF, such as a periodic SOF. For example, the reactionconditions may be tuned so the spacial orientation between the formedlinked molecular building blocks is uniform throughout the entire SOF,such that an SOF having a periodic structure is formed. In embodiments,the reaction components are selected by reverse synthesis of the linkedmolecular building blocks identified by the computer simulation ormaterials modeling.

In embodiments, reaction components (such as molecular building blocks,etc.,) identified as a result of the computer simulation or materialsmodeling are used to produce an SOF by tuning the reaction conditions ofthe process to produce the SOF so the spacial orientation between linkedmolecular building blocks is uniform throughout a portion or region ofthe SOF such that an SOF having a periodic portion or region is formed.

In embodiments, the linked molecular building blocks may be selectedsuch that there may be a high degree of molecular orbital overlapbetween molecular building blocks throughout the entire SOF. Inembodiments, a computer simulation or materials modeling may be used toidentify linked molecular building blocks that have a high degree ofmolecular orbital overlap between molecular building blocks throughoutthe entire SOF. In embodiments, the molecular building blocks, linkersand SOF type may be selected to allow for the production of efficientconduction pathways for electrons/holes. In embodiments, a computersimulation or materials modeling may be used to molecular buildingblocks, linkers and SOF type that allow for the production of efficientconduction pathways for electrons/holes.

In embodiments, computer simulation or materials modeling may be used toformulate the molecular-level structure of the SOF, such as, forexample, by estimating and/or maximizing the SOFs charge transportproperties. In embodiments, the computer simulation or materialsmodeling results may be used to select specific molecular buildingblocks, linkers and SOF type that substantially replicates the modeledmolecular-level structure of the SOF in at least a region of the SOF. Asused herein, the term “substantially replicates” refers to an tangiblereproduction of the simulated SOF that possesses the properties andcharacteristics of the simulated SOF, such as a dry SOF that possessesat least 80% of the predicted properties and characteristics of thesimulated SOF (e.g., a dry SOF with a mobility, degree of expectedmolecular orbital overlap, expected extent of uniformity regarding thespacial orientation of the building blocks, the band structure, oratomic-level stress (as well as other properties and characteristics)that is predicted for the simulated SOF) that is at least 80% of themobility, degree of expected molecular orbital overlap, expected extentof uniformity regarding the spacial orientation of the building blocks,the band structure, or atomic-level stress (as well as other propertiesand characteristics) that is predicted for the simulated SOF), or a drySOF that possesses at least 90% of the predicted properties andcharacteristics of the simulated. SOF, or a dry SOF that possesses atleast 95% of the predicted the properties and characteristics of thesimulated SOF, a dry SOF that possesses at least 95% of the predictedthe properties and characteristics of the simulated SOF.

In embodiments, the selected reaction components (such as molecularbuilding blocks, linkers, etc.,) identified as a result of the computersimulation or materials modeling are reacted to produce an SOF. Inembodiments, the reaction components (such as molecular building blocks,linkers, etc.,) identified as a result of the computer simulation ormaterials modeling may be reacted under conditions necessary in order toreplicate the modeled molecular-level structure of the SOF in at least apredetermined region of the SOF.

In embodiments, computer simulation or materials modeling may employdensity functional theory and quantum chemical calculations to calculatea preselected property or metric of the SOF. For example, computersimulation or materials modeling may employ density functional theoryand quantum chemical calculations to generate a density of statesdiagram (i.e. molecular orbital diagram for an extended solid) for thematerial and calculate the Fermi energy level. A general discussionregarding how to generate a density of states diagram and how the fermilevel would be calculated may be found in the following references (thedisclosures of which are hereby incorporated by reference in theirentireties:

-   Perdew, J. P.; Wang, Y. Phys. Rev. B., 33, 8800 (1986); Density    Functional Theory: A Tool for Chemistry, Politzer, P.;-   Seminario, J. M., Eds., Elsevier: Amsterdam (1995), and references    therein; Bradley, C. R.; Cracknell, A. P. The Mathematical Theory of    Symmetry in Solids, Clarendon Press: Oxford (1972);-   S. J. Clark, M. D. Segall, C. J. Pickard, P. J. Hasnip, M. J.    Probert, K. Refson, M. C. Payne Zeitschrift für Kristallographie 220    (5-6) pp. 567-570 (2005); and-   M. C. Payne, M. P. Teter and D. C. Allan, T. A. Arias, and J. D.    Joannopoulos, Rev. Mod. Phys. 64, 1045-4097 (1992).

In embodiments, computer simulation or materials modeling may employdensity functional theory and quantum chemical calculations to predicthigh mobility by assessing putative SOF structures for the location oftheir Fermi Levels in relation to its band structure. For example, inthe methods of the present disclosure, computer simulation or materialsmodeling may be used to identify materials (such as, for example, highmobility SOF materials) whose Fermi Level resides within a band and thuspossess a unique ability to transport charge.

In embodiments, computer simulation or materials modeling may include anab initio method designed to select specific molecular building blocks,linkers and SOF type and formulate the molecular-level structure of theSOF. In an ab initio method, the energy of the molecule and all of itsderivative values depend on the determination of the wavefunction. Theproblem is that the wavefunction is not a physical observable; that is,the wavefunction is purely a mathematical construct. In reality, thewavefunction is simply a statistical probability that the electron(s)will be at a specific place or part of the molecule (such as an SOF).Even though the wavefunction does not exist as a physical, observableproperty of an atom or molecule, the mathematical determination of thewavefunction (and with it, the atomic and molecular orbitals) may be agood predictor of various properties of the molecule, and in the case ofextended systems, a good predictor of bulk electronic structure.

In embodiments, computer simulation or materials modeling may include acomputational method based on Density Functional Theory. DensityFunctional Theory (DFT) is a computational method that derivesproperties of the molecule or collection of molecules based on adetermination of the electron density of the molecule. Unlike thewavefunction, which is not a physical reality but a mathematicalconstruct, electron density is a physical characteristic of allmolecules. A functional is defined as a function of a function, and theenergy of the molecule is a functional of the electron density. Theelectron density is a function with three variables—x-, y-, andz-position of the electrons. Unlike the wavefunction, which becomessignificantly more complicated as the number of electrons increases, thedetermination of the electron density is independent of the number ofelectrons.

Suitable types, or categories, of DFT computational methods that may beused in the methods of the present disclosure include Local DensityApproximation (LDA) methods, Gradient-Corrected (GC) methods, Hybridmethods, and the like. Local density approximation (LDA) methods assumethat the density of the molecule is uniform throughout the molecule.Gradient-corrected (GC) methods look to account for the non-uniformityof the electron density. Hybrid methods, as the name suggests, attemptto incorporate some of the more useful features from ab initio methods(specifically Hartree-Fock methods) with some of the improvements of DFTmathematics.

In embodiments, the specific molecular building blocks, linkers and SOFtype Periodic SOFs are selected by computer-aided design where chargetransport properties can be estimated using materials modeling software.For example, DFT methods are now standard in various software packages,including Gaussian, GAMESS, HyperChem, and Spartan, and MaterialsStudio. In addition, the user may customize a calculation to includeadvanced DFT methods. In embodiments, such software packages may includeMaterials Studio.

The Dmol3 module of Materials Studio was employed for the presentinvention. This module houses a suite of DFT-based tools for calculatingvarious properties of materials including electronic structure. In thecase of SOF systems a gradient correction method was usingPerdew-Burke-Ernzerhof correlation (PBE; Perdew, S. P.; Burke, K.;Ernzerhof, M. Phys. Rev. Lett., 77, 3865 (1996)), double numericalincluding d-funtions (DND) basis set, solving for 1×1×1 k-point set.

Metrical Parameters of SOFs

SOFs have any suitable aspect ratio. In embodiments, SOFs have aspectratios for instance greater than about 30:1 or greater than about 50:1,or greater than about 70:1, or greater than about 100:1, such as about1000:1. The aspect ratio of a SOF is defined as the ratio of its averagewidth or diameter (that is, the dimension next largest to its thickness)to its average thickness (that is, its shortest dimension). The term‘aspect ratio,’ as used here, is not bound by theory. The longestdimension of a SOF is its length and it is not considered in thecalculation of SOF aspect ratio.

Generally, SOFs have widths and lengths, or diameters greater than about500 micrometers, such as about 10 mm, or 30 mm. The SOFs have thefollowing illustrative thicknesses: about 10 Angstroms to about 250Angstroms, such as about 20 Angstroms to about 200 Angstroms, for amono-segment thick layer and about 20 nm to about 5 mm, about 50 nm toabout 10 mm for a multi-segment thick layer.

SOF dimensions may be measured using a variety of tools and methods. Fora dimension about 1 micrometer or less, scanning electron microscopy isthe preferred method. For a dimension about 1 micrometer or greater, amicrometer (or ruler) is the preferred method.

Multilayer SOFs

A SOF may comprise a single layer or a plurality of layers (that is,two, three or more layers) where the individual layers may be the sameor different types of SOFs, such as a periodic SOF, composite SOF,capped SOF, and/or combinations thereof. SOFs that are comprised of aplurality of layers may be physically joined (e.g., dipole and hydrogenbond) or chemically joined. Physically attached layers are characterizedby weaker interlayer interactions or adhesion; therefore physicallyattached layers may be susceptible to delamination from each other.Chemically attached layers are expected to have chemical bonds (e.g.,covalent or ionic bonds) or have numerous physical or intermolecular(supramolecular) entanglements that strongly link adjacent layers.

Therefore, delamination of chemically attached layers is much moredifficult. Chemical attachments between layers may be detected usingspectroscopic methods such as focusing infrared or Raman spectroscopy,or with other methods having spatial resolution that can detect chemicalspecies precisely at interfaces. In cases where chemical attachmentsbetween layers are different chemical species than those within thelayers themselves it is possible to detect these attachments withsensitive bulk analyses such as solid-state nuclear magnetic resonancespectroscopy or by using other bulk analytical methods.

In the embodiments, the SOF may be a single layer (mono-segment thick ormulti-segment thick) or multiple layers (each layer being mono-segmentthick or multi-segment thick). “Thickness” refers, for example, to thesmallest dimension of the film. As discussed above, in a SOF, segmentsare molecular units that are covalently bonded through linkers togenerate the molecular framework of the film. The thickness of the filmmay also be defined in terms of the number of segments that is countedalong that axis of the film when viewing the cross-section of the film.A “monolayer” SOF is the simplest case and refers, for example, to wherea film is one segment thick. A SOF where two or more segments existalong this axis is referred to as a “multi-segment” thick SOF.

An exemplary method for preparing physically attached multilayer SOFsincludes: (1) forming a base SOF layer that may be cured by a firstcuring cycle, and (2) forming upon the base layer a second reactive wetlayer followed by a second curing cycle and, if desired, repeating thesecond step to form a third layer, a forth layer and so on. Thephysically stacked multilayer SOFs may have thicknesses greater thanabout 20 Angstroms such as, for example, the following illustrativethicknesses: about 20 Angstroms to about 10 cm, such as about 1 nm toabout 10 mm, or about 0.1 mm Angstroms to about 5 mm. In principle thereis no limit with this process to the number of layers that may bephysically stacked.

In embodiments, a multilayer SOF is formed by a method for preparingchemically attached multilayer SOFs by: (1) forming a base SOF layerhaving functional groups present on the surface (or dangling functionalgroups) from a first reactive wet layer, and (2) forming upon the baselayer a second SOF layer from a second reactive wet layer that comprisesmolecular building blocks with functional groups capable of reactingwith the dangling functional groups on the surface of the base SOFlayer. In further embodiments, a capped SOF may serve as the base layerin which the functional groups present that were not suitable orcomplementary to participate in the specific chemical reaction to linktogether segments during the base layer SOF forming process may beavailable for reacting with the molecular building blocks of the secondlayer to from an chemically bonded multilayer SOF. If desired, theformulation used to form the second SOF layer should comprise molecularbuilding blocks with functional groups capable of reacting with thefunctional groups from the base layer as well as additional functionalgroups that will allow for a third layer to be chemically attached tothe second layer. The chemically stacked multilayer SOFs may havethicknesses greater than about 20 Angstroms such as, for example, thefollowing illustrative thicknesses: about 20 Angstroms to about 10 cm,such as about 1 nm to about 10 mm, or about 0.1 mm Angstroms to about 5mm. In principle there is no limit with this process to the number oflayers that may be chemically stacked.

In embodiments, the method for preparing chemically attached multilayerSOFs comprises promoting chemical attachment of a second SOF onto anexisting SOF (base layer) by using a small excess of one molecularbuilding block (when more than one molecular building block is present)during the process used to form the SOF (base layer) whereby thefunctional groups present on this molecular building block will bepresent on the base layer surface. The surface of base layer may betreated with an agent to enhance the reactivity of the functional groupsor to create an increased number of functional groups.

In an embodiment the dangling functional groups or chemical moietiespresent on the surface of an SOF or capped SOF may be altered toincrease the propensity for covalent attachment (or, alternatively, todisfavor covalent attachment) of particular classes of molecules orindividual molecules, such as SOFs, to a base layer or any additionalsubstrate or SOF layer. For example, the surface of a base layer, suchas an SOF layer, which may contain reactive dangling functional groups,may be rendered pacified through surface treatment with a cappingchemical, group. For example, a SOF layer having dangling hydroxylalcohol groups may be pacified by treatment with trimethylsiylchloridethereby capping hydroxyl groups as stable trimethylsilylethers.Alternatively, the surface of base layer may be treated with anon-chemically bonding agent, such as a wax, to block reaction withdangling functional groups from subsequent layers.

Molecular Building Block Symmetry

Molecular building block symmetry relates to the positioning offunctional groups (Fgs) around the periphery of the molecular buildingblock segments. Without being bound by chemical or mathematical theory,a symmetric molecular building block is one where positioning of Fgs maybe associated with the ends of a rod, vertexes of a regular geometricshape, or the vertexes of a distorted rod or distorted geometric shape.For example, the most symmetric option for molecular building blockscontaining four Fgs are those whose Fgs overlay with the corners of asquare or the apexes of a tetrahedron.

Use of symmetrical building blocks is practiced in embodiments of thepresent disclosure for two reasons: (1) the patterning of molecularbuilding blocks may be better anticipated because the linking of regularshapes is a better understood process in reticular chemistry, and (2)the complete reaction between molecular building blocks is facilitatedbecause for less symmetric building blocks errantconformations/orientations may be adopted which can possibly initiatenumerous linking defects within SOFs.

FIGS. 1A-O illustrate exemplary building blocks whose symmetricalelements are outlined. Such symmetrical elements are found in buildingblocks that may be used in the present disclosure.

Non-limiting examples of various classes of exemplary molecular entitiesthat may serve as molecular building blocks for SOFs of the presentdisclosure include building blocks containing a carbon or silicon atomiccore; building blocks containing alkoxy cores; building blockscontaining a nitrogen or phosphorous atomic core; building blockscontaining aryl cores; building blocks containing carbonate cores;building blocks containing carbocyclic-, carbobicyclic-, orcarbotricyclic core; and building blocks containing an oligothiophenecore.

In embodiments, a Type 1 SOF contains segments, which are not located atthe edges of the SOF, that are connected by linkers to at least threeother segments. For example, in embodiments the SOF comprises at leastone symmetrical building block selected from the group consisting ofideal triangular building blocks, distorted triangular building blocks,ideal tetrahedral building blocks, distorted tetrahedral buildingblocks, ideal square building blocks, and distorted square buildingblocks. In embodiments, Type 2 and 3 SOF contains at least one segmenttype, which are not located at the edges of the SOF, that are connectedby linkers to at least three other segments. For example, in embodimentsthe SOF comprises at least one symmetrical building block selected fromthe group consisting of ideal triangular building blocks, distortedtriangular building blocks, ideal tetrahedral building blocks, distortedtetrahedral building blocks, ideal square building blocks, and distortedsquare building blocks.

Practice of Linking Chemistry

In embodiments linking chemistry may occur wherein the reaction betweenfunctional groups produces a volatile byproduct that may be largelyevaporated or expunged from the SOF during or after the film formingprocess or wherein no byproduct is formed. Linking chemistry may beselected to achieve a SOF for applications where the presence of linkingchemistry byproducts is not desired. Linking chemistry reactions mayinclude, for example, condensation, addition/elimination, and additionreactions, such as, for example, those that produce esters, imines,ethers, carbonates, urethanes, amides, acetals, and silyl ethers.

In embodiments the linking chemistry via a reaction between functiongroups producing a non-volatile byproduct that largely remainsincorporated within the SOF after the film forming process. Linkingchemistry in embodiments may be selected to achieve a SOF forapplications where the presence of linking chemistry byproducts does notimpact the properties or for applications where the presence of linkingchemistry byproducts may alter the properties of a SOF (such as, forexample, the electroactive, hydrophobic or hydrophilic nature of theSOF). Linking chemistry reactions may include, for example,substitution, metathesis, and metal catalyzed coupling reactions, suchas those that produce carbon-carbon bonds.

For all linking chemistry the ability to control the rate and extent ofreaction between building blocks via the chemistry between buildingblock functional groups is an important aspect of the presentdisclosure. Reasons for controlling the rate and extent of reaction mayinclude adapting the film forming process for different coating methodsand tuning the microscopic arrangement of building blocks to achieve aperiodic SOF, as defined in earlier embodiments.

Innate Properties of COFs

COFs have innate properties such as high thermal stability (typicallyhigher than 400° C. under atmospheric conditions); poor solubility inorganic solvents (chemical stability), and porosity (capable ofreversible guest uptake). In embodiments, SOFs may also possess theseinnate properties.

Added Functionality of SOFs

Added functionality denotes a property that is not inherent toconventional COFs and may occur by the selection of molecular buildingblocks wherein the molecular compositions provide the addedfunctionality in the resultant SOF. Added functionality may arise uponassembly of molecular building blocks having an “inclined property” forthat added functionality. Added functionality may also arise uponassembly of molecular building blocks having no “inclined property” forthat added functionality but the resulting SOF has the addedfunctionality as a consequence of linking segments (S) and linkers intoa SOF. Furthermore, emergence of added functionality may arise from thecombined effect of using molecular building blocks bearing an “inclinedproperty” for that added functionality whose inclined property ismodified or enhanced upon linking together the segments and linkers intoa SOF.

An Inclined Property of a Molecular Building Block

The term “inclined property” of a molecular building block refers, forexample, to a property known to exist for certain molecular compositionsor a property that is reasonably identifiable by a person skilled in artupon inspection of the molecular composition of a segment. As usedherein, the terms “inclined property” and “added functionality” refer tothe same general property (e.g., hydrophobic, electroactive, etc.) but“inclined property” is used in the context of the molecular buildingblock and “added functionality” is used in the context of the SOF.

The hydrophobic (superhydrophobic), hydrophilic, lipophobic(superlipophobic), lipophilic, photochromic and/or electroactive(conductor, semiconductor, charge transport material) nature of an SOFare some examples of the properties that may represent an “addedfunctionality” of an SOF. These and other added functionalities mayarise from the inclined properties of the molecular building blocks ormay arise from building blocks that do not have the respective addedfunctionality that is observed in the SOF.

The term hydrophobic (superhydrophobic) refers, for example, to theproperty of repelling water, or other polar species such as methanol, italso means an inability to absorb water and/or to swell as a result.Furthermore, hydrophobic implies an inability to form strong hydrogenbonds to water or other hydrogen bonding species. Hydrophobic materialsare typically characterized by having water contact angles greater than90° and superhydrophobic materials have water contact angles greaterthan 150° as measured using a contact angle goniometer or relateddevice.

The term, hydrophilic refers, for example, to the property ofattracting, adsorbing, or absorbing water or other polar species, or asurface that is easily wetted by such species. Hydrophilic materials aretypically characterized by having less than 20° water contact angle asmeasured using a contact angle goniometer or related device.Hydrophilicity may also be characterized by swelling of a material bywater or other polar species, or a material that can diffuse ortransport water, or other polar species, through itself. Hydrophilicity,is further characterized by being able to form strong or numeroushydrogen bonds to water or other hydrogen bonding species.

The term lipophobic (oleophobic) refers, for example, to the property ofrepelling oil or other non-polar species such as alkanes, fats, andwaxes. Lipophobic materials are typically characterized by having oilcontact angles greater than 90° as measured using a contact anglegoniometer or related device.

The term lipophilic (oleophilic) refers, for example, to the propertyattracting oil or other non-polar species such as alkanes, fats, andwaxes or a surface that is easily wetted by such species. Lipophilicmaterials are typically characterized by having a low to nil oil contactangle as measured using, for example, a contact angle goniometer.Lipophilicity can also be characterized by swelling of a material byhexane or other non-polar liquids.

The term photochromic refers, for example, to the ability to demonstratereversible color changes when exposed to electromagnetic radiation. SOFcompositions containing photochromic molecules may be prepared anddemonstrate reversible color changes when exposed to electromagneticradiation. These SOFs may have the added functionality of photochromism.The robustness of photochromic SOFs may enable their use in manyapplications, such as photochromic SOFs for erasable paper, and lightresponsive films for window tinting/shading and eye wear. SOFcompositions may contain any suitable photochromic molecule, such as adifunctional photochromic molecules as SOF molecular building blocks(chemically bound into SOF structure), a monofunctional photochromicmolecules as SOF capping units (chemically bound into SOF structure, orunfunctionalized photochromic molecules in an SOF composite (notchemically bound into SOF structure). Photochromic SOFs may change colorupon exposure to selected wavelengths of light and the color change maybe reversible.

SOF compositions containing photochromic molecules that chemically bondto the SOF structure are exceptionally chemically and mechanicallyrobust photochromic materials. Such photochromic SOF materialsdemonstrate many superior properties, such as high number of reversiblecolor change processes, to available polymeric alternatives.

The term electroactive refers, for example, to the property to transportelectrical charge (electrons and/or holes). Electroactive materialsinclude conductors, semiconductors, and charge transport materials.Conductors are defined as materials that readily transport electricalcharge in the presence of a potential difference. Semiconductors aredefined as materials do not inherently conduct charge but may becomeconductive in the presence of a potential difference and an appliedstimuli, such as, for example, an electric field, electromagneticradiation, heat, and the like. Charge transport materials are defined asmaterials that can transport charge when charge is injected from anothermaterial such as, for example, a dye, pigment, or metal in the presenceof a potential difference.

Conductors may be further defined as materials that give a signal usinga potentiometer from about 0.1 to about 10⁷ S/cm.

Semiconductors may be further defined as materials that give a signalusing a potentiometer from about 10⁻⁶ to about 10⁴ S/cm in the presenceof applied stimuli such as, for example an electric field,electromagnetic radiation, heat, and the like. Alternatively,semiconductors may be defined as materials having electron and/or holemobility measured using time-of-flight techniques in the range of 10⁻¹⁰to about 10⁶ cm²V⁻¹ s⁻¹ when exposed to applied stimuli such as, forexample an electric field, electromagnetic radiation, heat, and thelike.

Charge transport materials may be further defined as materials that haveelectron and/or hole mobility measured using time-of-flight techniquesin the range of 10⁻¹⁰ to about 10⁶ cm²V⁻¹ s⁻¹. It should be noted thatunder some circumstances charge transport materials may be alsoclassified as semiconductors.

SOFs with hydrophobic added functionality may be prepared by usingmolecular building blocks with inclined hydrophobic properties and/orhave a rough, textured, or porous surface on the sub-micron to micronscale. A paper describing materials having a rough, textured, or poroussurface on the sub-micron to micron scale being hydrophobic was authoredby Cassie and Baxter (Cassie, A. B. D.; Baxter, S. Trans. Faraday Soc.,1944, 40, 546).

Molecular building blocks comprising or bearing highly-fluorinatedsegments have inclined hydrophobic properties and may lead to SOFs withhydrophobic added functionality. Highly-fluorinated segments are definedas the number of fluorine atoms present on the segment(s) divided by thenumber of hydrogen atoms present on the segment(s) being greater thanone. Fluorinated segments, which are not highly-fluorinated segments mayalso lead to SOFs with hydrophobic added functionality.

The above-mentioned fluorinated segments may include, for example,tetrafluorohydroquinone, perfluoroadipic acid hydrate,4,4′-(hexafluoroisopropylidene)diphthalic anhydride,4,4′-(hexafluoroisopropylidene)diphenol, and the like.

SOFs having a rough, textured, or porous surface on the sub-micron tomicron scale may also be hydrophobic. The rough, textured, or porous SOFsurface can result from dangling functional groups present on the filmsurface or from the structure of the SOF. The type of pattern and degreeof patterning depends on the geometry of the molecular building blocksand the linking chemistry efficiency. The feature size that leads tosurface roughness or texture is from about 100 nm to about 10 μm, suchas from about 500 nm to about 5 μm.

SOFs with hydrophilic added functionality may be prepared by usingmolecular building blocks with inclined hydrophilic properties and/orcomprising polar linking groups.

Molecular building blocks comprising segments bearing polar substituentshave inclined hydrophilic properties and may lead to SOFs withhydrophilic added functionality. The term polar substituents refers, forexample, to substituents that can form hydrogen bonds with water andinclude, for example, hydroxyl, amino, ammonium, and carbonyl (such asketone, carboxylic acid, ester, amide, carbonate, urea).

SOFs with electroactive added functionality may be prepared by usingmolecular building blocks with inclined electroactive properties and/orbe electroactive resulting from the assembly of conjugated segments andlinkers. The following sections describe molecular building blocks withinclined hole transport properties, inclined electron transportproperties, and inclined semiconductor properties.

SOFs with hole transport added functionality may be obtained byselecting segment cores such as, for example, triarylamines, hydrazones(U.S. Pat. No. 7,202,002 B2 to Tokarski et al.), and enamines (U.S. Pat.No. 7,416,824 B2 to Kondoh et al.) with the following generalstructures:

The segment core comprising a triarylamine being represented by thefollowing general formula:

wherein Ar¹, Ar², Ar³, Ar⁴ and Ar⁵ each independently represents asubstituted or unsubstituted aryl group, or Ar⁵ independently representsa substituted or unsubstituted arylene group, and k represents 0 or 1,wherein at least two of Ar¹, Ar², Ar³, Ar⁴ and Ar⁵ comprises a Fg(previously defined). Ar⁵ may be further defined as, for example, asubstituted phenyl ring, substituted/unsubstituted phenylene,substituted/unsubstituted monovalently linked aromatic rings such asbiphenyl, terphenyl, and the like, or substituted/unsubstituted fusedaromatic rings such as naphthyl, anthranyl, phenanthryl, and the like.

Segment cores comprising arylamines with hole transport addedfunctionality include, for example, aryl amines such as triphenylamine,N,N,N′,N′-tetraphenyl-(1,1′-biphenyl)-4,4′-diamine,N,N′-diphenyl-N,N′-bis(3-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine,N,N′-bis(4-butylphenyl)-N,N′-diphenyl-[p-terphenyl]-4,4″-diamine;hydrazones such as N-phenyl-N-methyl-3-(9-ethyl)carbazyl hydrazone and4-diethyl amino benzaldehyde-1,2-diphenyl hydrazone; and oxadiazolessuch as 2,5-bis(4-N,N′-diethylaminophenyl)-1,2,4-oxadiazole, stilbenes,and the like.

Molecular building blocks comprising triarylamine core segments withinclined hole transport properties may be derived from the list ofchemical structures including, for example, those listed below:

The segment core comprising a hydrazone being represented by thefollowing general formula:

wherein Ar¹, Ar², and Ar³ each independently represents an aryl groupoptionally containing one or more substituents, and R represents ahydrogen atom, an aryl group, or an alkyl group optionally containing asubstituent; wherein at least two of Ar¹, Ar², and Ar³ comprises a Fg(previously defined); and a related oxadiazole being represented by thefollowing general formula:

wherein Ar and Ar¹ each independently represent an aryl group thatcomprises a Fg (previously defined).

Molecular building blocks comprising hydrazone and oxadiazole coresegments with inclined hole transport properties may be derived from thelist of chemical structures including, for example, those listed below:

The segment core comprising an enamine being represented by thefollowing general formula:

wherein Ar¹, Ar², Ar³, and Ar⁴ each independently represents an arylgroup that optionally contains one or more substituents or aheterocyclic group that optionally contains one or more substituents,and R represents a hydrogen atom, an aryl group, or an alkyl groupoptionally containing a substituent; wherein at least two of Ar¹, Ar²,Ar³, and Ar⁴ comprises a Fg (previously defined).

Molecular building blocks comprising enamine core segments with inclinedhole transport properties may be derived from the list of chemicalstructures including, for example, those listed below:

SOFs with electron transport added functionality may be obtained byselecting segment cores comprising, for example, nitrofluorenones,9-fluorenylidene malonitriles, diphenoquinones, andnaphthalenetetracarboxylic diimides with the following generalstructures:

It should be noted that the carbonyl groups of diphenylquinones couldalso act as Fgs in the SOF forming process.

SOFs with semiconductor added functionality may be obtained by selectingsegment cores such as, for example, acenes,thiophenes/oligothiophenes/fused thiophenes, perylene bisimides, ortetrathiofulvalenes, and derivatives thereof with the following generalstructures:

The SOF may be a p-type semiconductor, n-type semiconductor or ambipolarsemiconductor. The SOF semiconductor type depends on the nature of themolecular building blocks. Molecular building blocks that possess anelectron donating property such as alkyl, alkoxy, aryl, and aminogroups, when present in the SOF, may render the SOF a p-typesemiconductor. Alternatively, molecular building blocks that areelectron withdrawing such as cyano, nitro, fluoro, fluorinated alkyl,and fluorinated aryl groups may render the SOF into the n-typesemiconductor.

Molecular building blocks comprising acene core segments with inclinedsemiconductor properties may be derived from the list of chemicalstructures including, for example, those listed below:

Molecular building blocks comprising thiophene/oligothiophene/fusedthiophene core segments with inclined semiconductor properties may bederived from the list of chemical structures including, for example,those listed below:

Examples of molecular building blocks comprising perylene bisimide coresegments with inclined semiconductor properties may be derived from thechemical structure below:

Molecular building blocks comprising tetrathiofulvalene core segmentswith inclined semiconductor properties may be derived from the list ofchemical structures including, for example, those listed below:

wherein Ar each independently represents an aryl group that optionallycontains one or more substituents or a heterocyclic group thatoptionally contains one or more substituents.

Similarly, the electroactivity of SOFs prepared by these molecularbuilding blocks will depend on the nature of the segments, nature of thelinkers, and how the segments are orientated within the SOF. Linkersthat favor preferred orientations of the segment moieties in the SOF areexpected to lead to higher electroactivity.

Process for Preparing an Ordered Structured Organic Film

The process for making SOFs, such as high mobility SOFs, which may haveperiodic regions or portions, typically comprises a number of activitiesor steps (set forth below) that may be performed in any suitablesequence or where two or more activities are performed simultaneously orin close proximity in time:

A process for preparing a structured organic film comprising:

(a) preparing a liquid-containing reaction mixture comprising aplurality of molecular building blocks each, comprising a segment and anumber of functional groups, and a pre-SOF;

(b) depositing the reaction mixture as a wet film;

(c) promoting a change of the wet film including the molecular buildingblocks to a dry film comprising the SOF comprising a plurality of thesegments and a plurality of linkers arranged as a covalent organicframework, wherein at a macroscopic level the covalent organic frameworkis a film;

(d) optionally removing the SOF from the coating substrate to obtain afree-standing SOF;

(e) optionally processing the free-standing SOF into a roll;

(f) optionally cutting and seaming the SOF into a belt; a

(g) optionally performing the above SOF formation process(es) upon anSOF (which was prepared by the above SOF formation process(es)) as asubstrate for subsequent SOF formation process(es); and

(h) optionally performing a computer simulation or materials modeling ofa various SOF compositions to select specific molecular building blocksand reaction components.

The process for making capped regions of the SOFs and/or composite SOFstypically comprises a similar number of activities or steps (set forthabove) that are used to make a non-capped SOF. The capping unit and/orsecondary component may be added during either step a, b or c, dependingthe desired distribution of the capping unit in the resulting SOF. Forexample, if it is desired that the capping unit and/or secondarycomponent distribution is substantially uniform over the resulting SOF,the capping unit may be added during step a. Alternatively, if, forexample, a more heterogeneous distribution of the capping unit and/orsecondary component is desired, adding the capping unit and/or secondarycomponent (such as by spraying it on the film formed during step b orduring the promotion step of step c) may occur during steps b and c.

The above activities or steps may be conducted at atmospheric, superatmospheric, or subatmospheric pressure. The term “atmospheric pressure”as used herein refers to a pressure of about 760 torr. The term “superatmospheric” refers to pressures greater than atmospheric pressure, butless than 20 atm. The term “subatmospheric pressure” refers to pressuresless than atmospheric pressure. In an embodiment, the activities orsteps may be conducted at or near atmospheric pressure. Generally,pressures of from about 0.1 atm to about 2 atm, such as from about 0.5atm to about 1.5 atm, or 0.8 atm to about 1.2 atm may be convenientlyemployed.

Process Action A: Preparation of the Liquid-Containing Reaction Mixture

The reaction mixture comprises a plurality of molecular building blocksthat are dissolved, suspended, or mixed in a liquid. The plurality ofmolecular building blocks may be of one type or two or more types. Whenone or more of the molecular building blocks is a liquid, the use of anadditional liquid is optional. Catalysts may optionally be added to thereaction mixture to enable pre-SOF formation and/or modify the kineticsof SOF formation during Action C described above. The term “pre-SOF” mayrefer to, for example, at least two molecular building blocks that havereacted and have a molecular weight higher than the starting molecularbuilding block and contain multiple functional groups capable ofundergoing further reactions with functional groups of other buildingblocks or pre-SOFs to obtain a SOF, which may be a substantiallydefect-free or defect-free SOF, and/or the ‘activation’ of molecularbuilding block functional groups that imparts enhanced or modifiedreactivity for the film forming process. Activation may includedissociation of a functional group moiety, pre-association with acatalyst, association with a solvent molecule, liquid, second solvent,second liquid, secondary component, or with any entity that modifiesfunctional group reactivity. In embodiments, pre-SOF formation mayinclude the reaction between molecular building blocks or the‘activation’ of molecular building block functional groups, or acombination of the two. The formation of the “pre-SOF” may be achievedby in a number of ways, such as heating the reaction mixture, exposureof the reaction mixture to UV radiation, or any other means of partiallyreacting the molecular building blocks and/or activating functionalgroups in the reaction mixture prior to deposition of the wet layer onthe substrate. Additives or secondary components may optionally be addedto the reaction mixture to alter the physical properties of theresulting SOF.

The reaction mixture components (molecular building blocks, optionally aliquid, optionally catalysts, and optionally additives) are combined ina vessel. The order of addition of the reaction mixture components mayvary; however, typically when a process for preparing a SOF includes apre-SOF or formation of a pre-SOF, the catalyst, when present, may beadded to the reaction mixture before depositing the reaction mixture asa wet film. In embodiments, the molecular building blocks may be reactedactinically, thermally, chemically or by any other means with or withoutthe presence of a catalyst to obtain a pre-SOF. The pre-SOF and themolecular building blocks formed in the absence of catalyst may be maybe heated in the liquid in the absence of the catalyst to aid thedissolution of the molecular building blocks and pre-SOFs. Inembodiments, the pre-SOF and the molecular building blocks formed in thepresence of catalyst may be may be heated at a temperature that does notcause significant further reaction of the molecular building blocksand/or the pre-SOFs to aid the dissolution of the molecular buildingblocks and pre-SOFs. The reaction mixture may also be mixed, stirred,milled, or the like, to ensure even distribution of the formulationcomponents prior to depositing the reaction mixture as a wet film.

In embodiments, the reaction mixture may be heated prior to beingdeposited as a wet film. This may aid the dissolution of one or more ofthe molecular building blocks and/or increase the viscosity of thereaction mixture by the partial reaction of the reaction mixture priorto depositing the wet layer to form pre-SOFs. For example, the weightpercent of molecular building blocks in the reaction mixture that areincorporated into pre-reacted molecular building blocks pre-SOFs may beless than 20%, such as about 15% to about 1%, or 10% to about 5%. Inembodiments, the molecular weight of the 95% pre-SOF molecules is lessthan 5,000 daltons, such as 2,500 daltons, or 1,000 daltons. Thepreparation of pre-SOFs may be used to increase the loading of themolecular building blocks in the reaction mixture.

In the case of pre-SOF formation via functional group activation, themolar percentage of functional groups that are activated may be lessthan 50%, such as about 30% to about 10%, or about 10% to about 5%.

In embodiments, the two methods of pre-SOF formation (pre-SOF formationby the reaction between molecular building blocks or pre-SOF formationby the ‘activation’ of molecular building block functional groups) mayoccur in combination and the molecular building blocks incorporated intopre-SOF structures may contain activated functional groups. Inembodiments, pre-SOF formation by the reaction between molecularbuilding blocks and pre-SOF formation by the ‘activation’ of molecularbuilding block functional groups may occur simultaneously.

In embodiments, the duration of pre-SOF formation lasts about 10 secondsto about 48 hours, such as about 30 seconds to about 12 hours, or about1 minute to 6 hours.

In particular embodiments, the reaction mixture needs to have aviscosity that will support the deposited wet layer. Reaction mixtureviscosities range from about 10 to about 50,000 cps, such as from about25 to about 25,000 cps or from about 50 to about 1000 cps.

The molecular building block and capping unit loading or “loading” inthe reaction mixture is defined as the total weight of the molecularbuilding blocks and optionally the capping units and catalysts dividedby the total weight of the reaction mixture. Building block loadings mayrange from about 3 to 100%, such as from about 5 to about 50%, or fromabout 15 to about 40%. In the case where a liquid molecular buildingblock is used as the only liquid component of the reaction mixture (i.e.no additional liquid is used), the building block loading would be about100%. The capping unit loading may be chosen, so as to achieve thedesired loading of the capping group. For example, depending on when thecapping unit is to be added to the reaction mixture, capping unitloadings may range, by weight, from about 3 to 80%, such as from about 5to about 50%, or from about 15 to about 40% by weight.

In embodiments, the theoretical upper limit for capping unit loading isthe molar amount of capping units that reduces the number of availablelinking groups to 2 per molecular building block in the liquid SOFformulation. In such a loading, substantial SOF formation may beeffectively inhibited by exhausting (by reaction with the respectivecapping group) the number of available linkable functional groups permolecular building block. For example, in such a situation (where thecapping unit loading is in an amount sufficient to ensure that the molarexcess of available linking groups is less than 2 per molecular buildingblock in the liquid SOF formulation), oligomers, linear polymers, andmolecular building blocks that are fully capped with capping units maypredominately form instead of an SOF.

In embodiments, the pre-SOF may be made from building blocks with one ormore of the added functionality selected from the group consisting ofhydrophobic added functionality, superhydrophobic added functionality,hydrophilic added functionality, lipophobic added functionality,superlipophobic added functionality, lipophilic added functionality,photochromic added functionality, and electroactive added functionality.In embodiments, the inclined property of the molecular building blocksis the same as the added functionality of the pre-SOF. In embodiments,the added functionality of the SOF is not an inclined property of themolecular building blocks.

Liquids used in the reaction mixture may be pure liquids, such assolvents, and/or solvent mixtures. Liquids are used to dissolve orsuspend the molecular building blocks and catalyst/modifiers in thereaction mixture. Liquid selection is generally based on balancing thesolubility/dispersion of the molecular building blocks and a particularbuilding block loading, the viscosity of the reaction mixture, and theboiling point of the liquid, which impacts the promotion of the wetlayer to the dry SOF. Suitable liquids may have boiling points fromabout 30 to about 300° C., such as from about 65° C. to about 250° C.,or from about 100° C. to about 180° C.

Liquids may include molecule classes such as alkanes (hexane, heptane,octane, nonane, decane, cyclohexane, cycloheptane, cyclooctane,decalin); mixed alkanes (hexanes, heptanes); branched alkanes(isooctane); aromatic compounds (toluene, o-, m-, p-xylene, mesitylene,nitrobenzene, benzonitrile, butylbenzene, aniline); ethers (benzyl ethylether, butyl ether, isoamyl ether, propyl ether); cyclic ethers(tetrahydrofuran, dioxane), esters (ethyl acetate, butyl acetate, butylbutyrate, ethoxyethyl acetate, ethyl propionate, phenyl acetate, methylbenzoate); ketones (acetone, methyl ethyl ketone, methyl isobutylketone,diethyl ketone, chloroacetone, 2-heptanone), cyclic ketones(cyclopentanone, cyclohexanone), amines (1°, 2°, or 3° amines such asbutylamine, diisopropylamine, triethylamine, diisoproylethylamine;pyridine); amides (dimethylformamide, N-methylpyrrolidinone,N,N-dimethylformamide); alcohols (methanol, ethanol, n-, propanol, n-,i-, t-butanol, 1-methoxy-2-propanol, hexanol, cyclohexanol, 3-pentanol,benzyl alcohol); nitriles (acetonitrile, benzonitrile, butyronitrile),halogenated aromatics (chlorobenzene, dichlorobenzene,hexafluorobenzene), halogenated alkanes (dichloromethane, chloroform,dichloroethylene, tetrachloroethane); and water.

Mixed liquids comprising a first solvent, second solvent, third solvent,and so forth may also be used in the reaction mixture. Two or moreliquids may be used to aid the dissolution/dispersion of the molecularbuilding blocks; and/or increase the molecular building block loading;and/or allow a stable wet film to be deposited by aiding the wetting ofthe substrate and deposition instrument; and/or modulate the promotionof the wet layer to the dry SOF. In embodiments, the second solvent is asolvent whose boiling point or vapor-pressure curve or affinity for themolecular building blocks differs from that of the first solvent. Inembodiments, a first solvent has a boiling point higher than that of thesecond solvent. In embodiments, the second solvent has a boiling pointequal to or less than about 100° C., such as in the range of from about30° C. to about 100° C., or in the range of from about 40° C. to about90° C., or about 50° C. to about 80° C.

In embodiments, the first solvent, or higher boiling point solvent, hasa boiling point equal to or greater than about 65° C., such as in therange of from about 80° C. to about 300° C., or in the range of fromabout 100° C. to about 250° C., or about 100° C. to about 180° C. Thehigher boiling point solvent may include, for example, the following(the value in parentheses is the boiling point of the compound):hydrocarbon solvents such as amylbenzene (202° C.), isopropylbenzene(152° C.), 1,2-diethylbenzene (183° C.), 1,3-diethylbenzene (181° C.),1,4-diethylbenzene (184° C.), cyclohexylbenzene (239° C.), dipentene(177° C.), 2,6-dimethylnaphthalene (262° C.), p-cymene (177° C.),camphor oil (160-185° C.), solvent naphtha (110-200° C.), cis-decalin(196° C.), trans-decalin (187° C.), decane (174° C.), tetralin (207°C.), turpentine oil (153-175° C.), kerosene (200-245° C.), dodecane(216° C.), dodecylbenzene (branched), and so forth; ketone and aldehydesolvents such as acetophenone (201.7° C.), isophorone (215.3° C.),phorone (198-199° C.), methylcyclohexanone (169.0-170.5° C.), methyln-heptyl ketone (195.3° C.), and so forth; ester solvents such asdiethyl phthalate (296.1° C.), benzyl acetate (215.5° C.),γ-butyrolactone (204° C.), dibutyl oxalate (240° C.), 2-ethylhexylacetate (198.6° C.), ethyl benzoate (213.2° C.), benzyl formate (203°C.), and so forth; diethyl sulfate (208° C.), sulfolane (285° C.), andhalohydrocarbon solvents; etherified hydrocarbon solvents; alcoholsolvents; ether/acetal solvents; polyhydric alcohol solvents; carboxylicanhydride solvents; phenolic solvents; water; and silicone solvents.

The ratio of the mixed liquids may be established by one skilled in theart. The ratio of liquids a binary mixed liquid may be from about 1:1 toabout 99:1, such as from about 1:10 to about 10:1, or about 1:5 to about5:1, by volume. When n liquids are used, with n ranging from about 3 toabout 6, the amount of each liquid ranges from about 1% to about 95%such that the sum of each liquid contribution equals 100%.

In embodiments, the mixed liquid comprises at least a first and a secondsolvent with different boiling points. In further embodiments, thedifference in boiling point between the first and the second solvent maybe from about nil to about 150° C., such as from nil to about 50° C. Forexample, the boiling point of the first solvent may exceed the boilingpoint of the second solvent by about 1° C. to about 100° C., such as byabout 5° C. to about 100° C., or by about 10° C. to about 50° C. Themixed liquid may comprise at least a first and a second solvent withdifferent vapor pressures, such as combinations of high vapor pressuresolvents and/or low vapor pressure solvents. The term “high vaporpressure solvent” refers to, for example, a solvent having a vaporpressure of at least about 1 kPa, such as about 2 kPa, or about 5 kPa.The term “low vapor pressure solvent” refers to, for example, a solventhaving a vapor pressure of less than about 1 kPa, such as about 0.9 kPa,or about 0.5 kPa. In embodiments, the first solvent may be a low vaporpressure solvent such as, for example, terpineol, diethylene glycol,ethylene glycol, hexylene glycol, N-methyl-2-pyrrolidone, andtri(ethylene glycol)dimethyl ether. A high vapor pressure solvent allowsrapid removal of the solvent by drying and/or evaporation attemperatures below the boiling point. High vapor pressure solvents mayinclude, for example, acetone, tetrahydrofuran, toluene, xylene,ethanol, methanol, 2-butanone and water.

In embodiments where mixed liquids comprising a first solvent, secondsolvent, third solvent, and so forth are used in the reaction mixture,promoting the change of the wet film and forming the dry SOF maycomprise, for example, heating the wet film to a temperature above theboiling point of the reaction mixture to form the dry SOF film; orheating the wet film to a temperature above the boiling point of thesecond solvent (below the temperature of the boiling point of the firstsolvent) in order to remove the second solvent while substantiallyleaving the first solvent and then after substantially removing thesecond solvent, removing the first solvent by heating the resultingcomposition at a temperature either above or below the boiling point ofthe first solvent to form the dry SOF film; or heating the wet filmbelow the boiling point of the second solvent in order to remove thesecond solvent (which is a high vapor pressure solvent) whilesubstantially leaving the first solvent and, after removing the secondsolvent, removing the first solvent by heating the resulting compositionat a temperature either above or below the boiling point of the firstsolvent to form the dry SOF film.

The term “substantially removing” refers to, for example, the removal ofat least 90% of the respective solvent, such as about 95% of therespective solvent. The term “substantially leaving” refers to, forexample, the removal of no more than 2% of the respective solvent, suchas removal of no more than 1% of the respective solvent.

These mixed liquids may be used to slow or speed up the rate ofconversion of the wet layer to the SOF in order to manipulate thecharacteristics of the SOFs. For example, in condensation andaddition/elimination linking chemistries, liquids such as water, 1°, 2°,or 3° alcohols (such as methanol, ethanol, propanol, isopropanol,butanol, 1-methoxy-2-propanol, tert-butanol) may be used.

Optionally a catalyst may be present in the reaction mixture to assistthe promotion of the wet layer to the dry SOF. Selection and use of theoptional catalyst depends on the functional groups on the molecularbuilding blocks. Catalysts may be homogeneous (dissolved) orheterogeneous (undissolved or partially dissolved) and include Brönstedacids (HCl (aq), acetic acid, p-toluenesulfonic acid, amine-protectedp-toluenesulfonic acid such as pyrridium p-toluenesulfonate,trifluoroacetic acid); Lewis acids (boron trifluoroetherate, aluminumtrichloride); Brönsted bases (metal hydroxides such as sodium hydroxide,lithium hydroxide, potassium hydroxide; 1°, 2°, or 3° amines such asbutylamine, diisopropylamine, triethylamine, diisoproylethylamine);Lewis bases (N,N-dimethyl-4-aminopyridine); metals (Cu bronze); metalsalts (FeCl₃, AuCl₃); and metal complexes (ligated palladium complexes,ligated ruthenium catalysts). Typical catalyst loading ranges from about0.01% to about 25%, such as from about 0.1% to about 5% of the molecularbuilding block loading in the reaction mixture. The catalyst may or maynot be present in the final SOF composition.

Optionally additives or secondary components, such as dopants, may bepresent in the reaction mixture and wet layer. Such additives orsecondary components may also be integrated into a dry SOF. Additives orsecondary components can be homogeneous or heterogeneous in the reactionmixture and wet layer or in a dry SOF. The terms “additive” or“secondary component,” refer, for example, to atoms or molecules thatare not covalently bound in the SOF, but are randomly distributed in thecomposition. In embodiments, secondary components such as conventionaladditives may be used to take advantage of the known propertiesassociated with such conventional additives. Such additives may be usedto alter the physical properties of the SOF such as electricalproperties (conductivity, semiconductivity, electron transport, holetransport), surface energy (hydrophobicity, hydrophilicity), tensilestrength, and thermal conductivity; such additives may include impactmodifiers, reinforcing fibers, lubricants, antistatic agents, couplingagents, wetting agents, antifogging agents, flame retardants,ultraviolet stabilizers, antioxidants, biocides, dyes, pigments,odorants, deodorants, nucleating agents and the like.

In embodiments, the SOF may contain antioxidants as a secondarycomponent to protect the SOF from oxidation. Examples of suitableantioxidants include (1) N,N′-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy hydrocinnamamide) (IRGANOX 1098,available from Ciba-Geigy Corporation), (2)2,2-bis(4-(2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy))ethoxyphenyl)propane (TOPANOL-205, available from ICI America Corporation), (3)tris(4-tert-butyl-3-hydroxy-2,6-dimethyl benzyl) isocyanurate (CYANOX1790, 41,322-4, LTDP, Aldrich D12, 840-6), (4) 2,2′-ethylidenebis(4,6-di-tert-butylphenyl) fluoro phosphonite (ETHANOX-398, availablefrom Ethyl Corporation), (5)tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenyl diphosphonite (ALDRICH46, 852-5; hardness value 90), (6) pentaerythritol tetrastearate (TCIAmerica #PO739), (7) tributylammonium hypophosphite (Aldrich 42,009-3),(8) 2,6-di-tert-butyl-4-methoxyphenol (Aldrich 25, 106-2), (9)2,4-di-tert-butyl-6-(4-methoxybenzyl) phenol (Aldrich 23,008-1), (10)4-bromo-2,6-dimethylphenol (Aldrich 34, 951-8), (11)4-bromo-3,5-didimethylphenol (Aldrich B6, 420-2), (12)4-bromo-2-nitrophenol (Aldrich 30, 987-7), (13) 4-(diethylaminomethyl)-2,5-dimethylphenol (Aldrich 14, 668-4), (14)3-dimethylaminophenol (Aldrich D14, 400-2), (15)2-amino-4-tert-amylphenol (Aldrich 41, 258-9), (16)2,6-bis(hydroxymethyl)-p-cresol (Aldrich 22, 752-8), (17)2,2′-methylenediphenol (Aldrich B4, 680-8), (18)5-(diethylamino)-2-nitrosophenol (Aldrich 26, 951-4), (19)2,6-dichloro-4-fluorophenol (Aldrich 28, 435-1), (20) 2,6-dibromo fluorophenol (Aldrich 26,003-7), (21) a trifluoro-o-cresol (Aldrich 21,979-7), (22) 2-bromo-4-fluorophenol (Aldrich 30, 246-5), (23)4-fluorophenol (Aldrich F1, 320-7), (24)4-chlorophenyl-2-chloro-1,1,2-tri-fluoroethyl sulfone (Aldrich 13,823-1), (25) 3,4-difluoro phenylacetic acid (Aldrich 29,043-2), (26)3-fluorophenylacetic acid (Aldrich 24, 804-5), (27) 3,5-difluorophenylacetic acid (Aldrich 29,044-0), (28) 2-fluorophenylacetic acid(Aldrich 20, 894-9), (29) 2,5-bis(trifluoromethyl) benzoic acid (Aldrich32, 527-9), (30) ethyl-2-(4-(4-(trifluoromethyl)phenoxy)phenoxy)propionate (Aldrich 25,074-0), (31) tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenyl diphosphonite (Aldrich 46, 852-5), (32)4-tert-amyl phenol (Aldrich 15, 384-2), (33)3-(2H-benzotriazol-2-yl)-4-hydroxy phenethylalcohol (Aldrich 43,071-4),NAUGARD 76, NAUGARD 445, NAUGARD 512, and NAUGARD 524 (manufactured byUniroyal Chemical Company), and the like, as well as mixtures thereof.The antioxidant, when present, may be present in the SOF composite inany desired or effective amount, such as from about 0.25 percent toabout 10 percent by weight of the SOF or from about 1 percent to about 5percent by weight of the SOF.

In embodiments, the SOF may further comprise any suitable polymericmaterial known in the art as a secondary component, such aspolycarbonates, acrylate polymers, vinyl polymers, cellulose polymers,polyesters, polysiloxanes, polyamides, polyurethanes, polystyrenes,polystyrene, polyolefins, fluorinated hydrocarbons (fluorocarbons), andengineered resins as well as block, random or alternating copolymersthereof. The SOF composite may comprise homopolymers, higher orderpolymers, or mixtures thereof, and may comprise one species of polymericmaterial or mixtures of multiple species of polymeric material, such asmixtures of two, three, four, five or more multiple species of polymericmaterial. In embodiments, suitable examples of the about polymersinclude, for example, crystalline and amorphous polymers, or a mixturesthereof. In embodiments, the polymer is a fluoroelastomer.

Suitable fluoroelastomers are those described in detail in U.S. Pat.Nos. 5,166,031, 5,281,506, 5,366,772, 5,370,931, 4,257,699, 5,017,432and 5,061,965, the disclosures each of which are incorporated byreference herein in their entirety. The amount of fluoroelastomercompound present in the SOF, in weight percent total solids, is fromabout 1 to about 50 percent, or from about 2 to about 10 percent byweight of the SOF. Total solids, as used herein, includes the amount ofsecondary components and SOF.

In embodiments, examples of styrene-based monomer and acrylate-basedmonomers include, for example, poly(styrene-alkyl acrylate),poly(styrene-1,3-diene), poly(styrene-alkyl methacrylate),poly(styrene-alkyl acrylate-acrylic acid),poly(styrene-1,3-diene-acrylic acid), poly(styrene-alkylmethacrylate-acrylic acid), poly(alkyl methacrylate-alkyl acrylate),poly(alkyl methacrylate-aryl acrylate), poly(aryl methacrylate-alkylacrylate), poly(alkyl methacrylate-acrylic acid), poly(styrene-alkylacrylate-acrylonitrile-acrylic acid),poly(styrene-1,3-diene-acrylonitrile-acrylic acid), poly(alkylacrylate-acrylonitrile-acrylic acid), poly(styrene-butadiene),poly(methylstyrene-butadiene), poly(methyl methacrylate-butadiene),poly(ethyl methacrylate-butadiene), poly(propyl methacrylate-butadiene),poly(butyl methacrylate-butadiene), poly(methyl acrylate-butadiene),poly(ethyl acrylate-butadiene), poly(propyl acrylate-butadiene),poly(butyl acrylate-butadiene), poly(styrene-isoprene),poly(methylstyrene-isoprene), poly(methyl methacrylate-isoprene),poly(ethyl methacrylate-isoprene), poly(propyl methacrylate-isoprene),poly(butyl methacrylate-isoprene), poly(methyl acrylate-isoprene),poly(ethyl acrylate-isoprene), poly(propyl acrylate-isoprene), andpoly(butyl acrylate-isoprene); poly(styrene-propyl acrylate),poly(styrene-butyl acrylate), poly(styrene-butadiene-acrylic acid),poly(styrene-butadiene-methacrylic acid),poly(styrene-butadiene-acrylonitrile-acrylic acid), poly(styrene-butylacrylate-acrylic acid), poly(styrene-butyl acrylate-methacrylic acid),poly(styrene-butyl acrylate-acrylonitrile), poly(styrene-butylacrylate-acrylonitrile-acrylic acid), and other similar polymers.

Further examples of the various polymers that are suitable for use as asecondary component in SOFs include polyethylene terephthalate,polybutadienes, polysulfones, polyarylethers, polyarylsulfones,polyethersulfones, polycarbonates, polyethylenes, polypropylenes,polydecene, polydodecene, polytetradecene, polyhexadecene, polyoctadene,and polycyclodecene, polyolefin copolymers, mixtures of polyolefins,functional polyolefins, acidic polyolefins, branched polyolefins,polymethylpentenes, polyphenylene sulfides, polyvinyl acetates,polyvinylbutyrals, polysiloxanes, polyacrylates, polyvinyl acetals,polyamides, polyimides, polystyrene and acrylonitrile copolymers,polyvinylchlorides, polyvinyl alcohols, poly-N-vinylpyrrolidinone)s,vinylchloride and vinyl acetate copolymers, acrylate copolymers,poly(amideimide), styrene-butadiene copolymers,vinylidenechloride-vinylchloride copolymers,vinylacetate-vinylidenechloride copolymers, polyvinylcarbazoles,polyethylene-terephthalate, polypropylene-terephthalate,polybutylene-terephthalate, polypentylene-terephthalate,polyhexylene-terephthalate, polyheptadene-terephthalate,polyoctalene-terephthalate, polyethylene-sebacate, polypropylenesebacate, polybutylene-sebacate, polyethylene-adipate,polypropylene-adipate, polybutylene-adipate, polypentylene-adipate,polyhexylene-adipate, polyheptadene-adipate, polyoctalene-adipate,polyethylene-glutarate, polypropylene-glutarate, polybutylene-glutarate,polypentylene-glutarate, polyhexylene-glutarate,polyheptadene-glutarate, polyoctalene-glutarate polyethylene-pimelate,polypropylene-pimelate, polybutylene-pimelate, polypentylene-pimelate,polyhexylene-pimelate, polyheptadene-pimelate, poly(propoxylatedbisphenol-fumarate), poly(propoxylated bisphenol-succinate),poly(propoxylated bisphenol-adipate), poly(propoxylatedbisphenol-glutarate), SPAR™ (Dixie Chemicals), BECKOSOL™ (ReichholdChemical Inc), ARAKOTE™ (Ciba-Geigy Corporation), HETRON™ (AshlandChemical), PARAPLEX™ (Rohm & Hass), POLYLITE™ (Reichhold Chemical Inc),PLASTHALL™ (Rohm & Hass), CYGAL™ (American Cyanamide), ARMCO™ (ArmcoComposites), ARPOL™ (Ashland Chemical), CELANEX™ (Celanese Eng), RYNITE™(DuPont), STYPOL™ (Freeman Chemical Corporation) mixtures thereof andthe like.

In embodiments, the secondary components, including polymers may bedistributed homogeneously, or heterogeneously, such as in a linear ornonlinear gradient in the SOF. In embodiments, the polymers may beincorporated into the SOF in the form of a fiber, or a particle whosesize may range from about 50 nm to about 2 mm. The polymers, whenpresent, may be present in the SOF composite in any desired or effectiveamount, such as from about 1 percent to about 50 percent by weight ofthe SOF or from about 1 percent to about 15 percent by weight of theSOF.

In embodiments, the SOF may further comprise carbon nanotubes ornanofiber aggregates, which are microscopic particulate structures ofnanotubes, as described in U.S. Pat. Nos. 5,165,909; 5,456,897;5,707,916; 5,877,110; 5,110,693; 5,500,200 and 5,569,635, all of whichare hereby entirely incorporated by reference.

In embodiments, the SOF may further comprise metal particles as asecondary component; such metal particles include noble and non-noblemetals and their alloys. Examples of suitable noble metals include,aluminum, titanium, gold, silver, platinum, palladium and their alloys.Examples of suitable non-noble metals include, copper, nickel, cobalt,lead, iron, bismuth, zinc, ruthenium, rhodium, rubidium, indium, andtheir alloys. The size of the metal particles may range from about 1 nmto 1 mm and their surfaces may be modified by stabilizing molecules ordispersant molecules or the like. The metal particles, when present, maybe present in the SOF composite in any desired or effective amount, suchas from about 0.25 percent to about 70 percent by weight of the SOF orfrom about 1 percent to about 15 percent by weight of the SOF.

In embodiments, the SOF may further comprise oxides and sulfides assecondary components. Examples of suitable metal oxides include,titanium dioxide (titania, rutile and related polymorphs), aluminumoxide including alumina, hydradated alumina, and the like, silicon oxideincluding silica, quartz, cristobalite, and the like, aluminosilicatesincluding zeolites, talcs, and clays, nickel oxide, iron oxide, cobaltoxide. Other examples of oxides include glasses, such as silica glass,borosilicate glass, aluminosilicate glass and the like. Examples ofsuitable sulfides include nickel sulfide, lead sulfide, cadmium sulfide,tin sulfide, and cobalt sulfide. The diameter of the oxide and sulfidematerials may range from about 50 nm to 1 mm and their surfaces may bemodified by stabilizing molecules or dispersant molecules or the like.The oxides, when present, may be present in the SOF composite in anydesired or effective amount, such as from about 0.25 percent to about 20percent by weight of the SOF or from about 1 percent to about 15 percentby weight of the SOF.

In embodiments, the SOF may further comprise metalloid or metal-likeelements from the periodic table. Examples of suitable metalloidelements include, silicon, selenium, tellurium, tin, lead, germanium,gallium, arsenic, antimony and their alloys or intermetallics. The sizeof the metal particles may range from about 10 nm to 1 mm and theirsurfaces may be modified by stabilizing molecules or dispersantmolecules or the like. The metalloid particles, when present, may bepresent in the SOF composite in any desired or effective amount, such asfrom about 0.25 percent to about 10 percent by weight of the SOF or fromabout 1 percent to about 5 percent by weight of the SOF.

In embodiments, the SOF may further comprise hole transport molecules orelectron acceptors as a secondary component, such charge transportmolecules include for example a positive hole transporting materialselected from compounds having in the main chain or the side chain apolycyclic aromatic ring such, as anthracene, pyrene, phenanthrene,coronene, and the like, or a nitrogen-containing hetero ring such asindole, carbazole, oxazole, isoxazole, thiazole, imidazole, pyrazole,oxadiazole, pyrazoline, thiadiazole, triazole, and hydrazone compounds.Typical hole transport materials include electron donor materials, suchas carbazole; N-ethyl carbazole; N-isopropyl carbazole; N-phenylcarbazole; tetraphenylpyrene; 1-methylpyrene; perylene; chrysene;anthracene; tetraphene; 2-phenyl naphthalene; azopyrene; 1-ethyl pyrene;acetyl pyrene; 2,3-benzochrysene; 2,4-benzopyrene; 1,4-bromopyrene; poly(N-vinylcarbazole); poly(vinylpyrene); poly(vinyltetraphene);poly(vinyltetracene) and poly(vinylperylene). Suitable electrontransport materials include electron acceptors such as2,4,7-trinitro-9-fluorenone; 2,4,5,7-tetranitro-fluorenone;dinitroanthracene; dinitroacridene; tetracyanopyrene;dinitroanthraquinone; and butylcarbonylfluorenemalononitrile, see U.S.Pat. No. 4,921,769 the disclosure of which is incorporated herein byreference in its entirety. Other hole transporting materials includearylamines described in U.S. Pat. No. 4,265,990 the disclosure of whichis incorporated herein by reference in its entirety, such asN,N′-diphenyl-N,N′-bis(alkylphenyl)-(1,1′-biphenyl)-4,4′-diamine whereinalkyl is selected from the group consisting of methyl, ethyl, propyl,butyl, hexyl, and the like. Hole transport molecules of the typedescribed in, for example, U.S. Pat. Nos. 4,306,008; 4,304,829;4,233,384; 4,115,116; 4,299,897; 4,081,274, and 5,139,910, the entiredisclosures of each are incorporated herein by reference. Other knowncharge transport layer molecules may be selected, reference for exampleU.S. Pat. Nos. 4,921,773 and 4,464,450 the disclosures of which areincorporated herein by reference in their entireties. The hole transportmolecules or electron acceptors, when present, may be present in the SOFcomposite in any desired or effective amount, such as from about 0.25percent to about 50 percent by weight of the SOF or from about 1 percentto about 20 percent by weight of the SOF.

In embodiments, the SOF may further comprise biocides as a secondarycomponent. Biocides may be present in amounts of from about 0.1 to about1.0 percent by weight of the SOF. Suitable biocides include, forexample, sorbic acid, 1-(3-chloroallyl)-3,5,7-triaza-1-azoniaadamantanechloride, commercially available as DOWICIL 200 (Dow Chemical Company),vinylene-bis thiocyanate, commercially available as CYTOX 3711 (AmericanCyanamid Company), disodium ethylenebis-dithiocarbamate, commerciallyavailable as DITHONE D14 (Rohm & Haas Company),bis(trichloromethyl)sulfone, commercially available as BIOCIDE N-1386(Stauffer Chemical Company), zinc pyridinethione, commercially availableas zinc omadine (Olin Corporation), 2-bromo-t-nitropropane-1,3-diol,commercially available as ONYXIDE 500 (Onyx Chemical Company), BOSQUATMB50 (Louza, Inc.), and the like.

In embodiments, the SOF may further comprise small organic molecules asa secondary component; such small organic molecules include thosediscussed above with respect to the first and second solvents. The smallorganic molecules, when present, may be present in the SOF in anydesired or effective amount, such as from about 0.25 percent to about 50percent by weight of the SOF or from about 1 percent to about 10 percentby weight of the SOF.

When present, the secondary components or additives may each, or incombination, be present in the composition in any desired or effectiveamount, such as from about 1 percent to about 50 percent by weight ofthe composition or from about 1 percent to about 20 percent by weight ofthe composition.

SOFs may be modified with secondary components (dopants and additives,such as, hole transport molecules (mTBD), polymers (polystyrene),nanoparticles (C60 Buckminster fullerene), small organic molecules(biphenyl), metal particles (copper micropowder), and electron acceptors(quinone)) to give composite structured organic films. Secondarycomponents may be introduced to the liquid formulation that is used togenerate a wet film in which a change is promoted to form the SOF.Secondary components (dopants, additives, etc.) may either be dissolvedor undissolved (suspended) in the reaction mixture. Secondary componentsare not bonded into the network of the film. For example, a secondarycomponent may be added to a reaction mixture that contains a pluralityof building blocks having four methoxy groups (—OMe) on a segment, suchas N4,N4,N4′,N4′-tetra-p-tolylbiphenyl-4,4′-diamine, which uponpromotion of a change in the wet film, exclusively react with the twoalcohol (—OH) groups on a building block, such as 1,4-benzenedimethanol,which contains a p-xylyl segment. The chemistry that is occurring tolink building blocks is an acid catalyzed transetherfication reaction.Because —OH groups will only react with —OMe groups (and vice versa) andnot with the secondary component, these molecular building blocks canonly follow one pathway. Therefore, the SOF is programmed to ordermolecules in a way that leaves the secondary component incorporatedwithin and/or around the SOF structure. This ability to patternmolecules and incorporate secondary components affords superiorperformance and unprecedented control over properties compared toconventional polymers and available alternatives.

Optionally additives or secondary components, such as dopants, may bepresent in the reaction mixture and wet layer. Such additives orsecondary components may also be integrated into a dry SOF. Additives orsecondary components can be homogeneous or heterogeneous in the reactionmixture and wet layer or in a dry SOF. In contrast to capping units, theterms “additive” or “secondary component,” refer, for example, to atomsor molecules that are not covalently bound in the SOF, but are randomlydistributed in the composition. Suitable secondary components andadditives are described in U.S. patent application Ser. No. 12/716,324,entitled “Composite Structured Organic Films,” the disclosure of whichis totally incorporated herein by reference in its entirety.

In embodiments, the secondary components may have similar or disparateproperties to accentuate or hybridize (synergistic effects orameliorative effects as well as the ability to attenuate inherent orinclined properties of the capped SOF) the intended property of thecapped SOF to enable it to meet performance targets. For example, dopingthe capped SOFs with antioxidant compounds will extend the life of thecapped SOF by preventing chemical degradation pathways. Additionally,additives maybe added to improve the morphological properties of thecapped SOF by tuning the reaction occurring during the promotion of thechange of the reaction mixture to form the capped. SOF.

Process Action B: Depositing the Reaction Mixture as a Wet Film

The reaction mixture may be applied as a wet film to a variety ofsubstrates using a number of liquid deposition techniques. The thicknessof the SOF is dependant on the thickness of the wet film and themolecular building block loading in the reaction mixture. The thicknessof the wet film is dependent on the viscosity of the reaction mixtureand the method used to deposit the reaction mixture as a wet film.

Substrates include, for example, polymers, papers, metals and metalalloys, doped and undoped forms of elements from Groups III-VI of theperiodic table, metal oxides, metal chalcogenides, and previouslyprepared SOFs or capped SOFs. Examples of polymer film substratesinclude polyesters, polyolefins, polycarbonates, polystyrenes,polyvinylchloride, block and random copolymers thereof, and the like.Examples of metallic surfaces include metallized polymers, metal foils,metal plates; mixed material substrates such as metals patterned ordeposited on polymer, semiconductor, metal oxide, or glass substrates.Examples of substrates comprised of doped and undoped elements fromGroups III-VI of the periodic table include, aluminum, silicon, siliconn-doped with phosphorous, silicon p-doped with boron, tin, galliumarsenide, lead, gallium indium phosphide, and indium. Examples of metaloxides include silicon dioxide, titanium dioxide, indium tin oxide, tindioxide, selenium dioxide, and alumina. Examples of metal chalcogenidesinclude cadmium sulfide, cadmium telluride, and zinc selenide.Additionally, it is appreciated that chemically treated or mechanicallymodified forms of the above substrates remain within the scope ofsurfaces which may be coated with the reaction mixture.

In embodiments, the substrate may be composed of, for example, silicon,glass plate, plastic film or sheet. For structurally flexible devices, aplastic substrate such as polyester, polycarbonate, polyimide sheets andthe like may be used. The thickness of the substrate may be from around10 micrometers to over 10 millimeters with an exemplary thickness beingfrom about 50 to about 100 micrometers, especially for a flexibleplastic substrate, and from about 1 to about 10 millimeters for a rigidsubstrate such as glass or silicon.

The reaction mixture may be applied to the substrate using a number ofliquid deposition techniques including, for example, spin coating, bladecoating, web coating, dip coating, cup coating, rod coating, screenprinting, ink jet printing, spray coating, stamping and the like. Themethod used to deposit the wet layer depends on the nature, size, andshape of the substrate and the desired wet layer thickness. Thethickness of the wet layer can range from about 10 nm to about 5 mm,such as from about 100 nm to about 1 mm, or from about 1 μm to about 500μm.

In embodiments, the capping unit and/or secondary component may beintroduced following completion of the above described process action B.The incorporation of the capping unit and/or secondary component in thisway may be accomplished by any means that serves to distribute thecapping unit and/or secondary component homogeneously, heterogeneously,or as a specific pattern over the wet film. Following introduction ofthe capping unit and/or secondary component subsequent process actionsmay be carried out resuming with process action C.

For example, following completion of process action B (i.e., after thereaction mixture may be applied to the substrate), capping unit(s)and/or secondary components (dopants, additives, etc.) may be added tothe wet layer by any suitable method, such as by distributing (e.g.,dusting, spraying, pouring, sprinkling, etc, depending on whether thecapping unit and/or secondary component is a particle, powder or liquid)the capping unit(s) and/or secondary component on the top the wet layer.The capping units and/or secondary components may be applied to theformed wet layer in a homogeneous or heterogeneous manner, includingvarious patterns, wherein the concentration or density of the cappingunit(s) and/or secondary component is reduced in specific areas, such asto form a pattern of alternating bands of high and low concentrations ofthe capping unit(s) and/or secondary component of a given width on thewet layer. In embodiments, the application of the capping unit(s) and/orsecondary component to the top of the wet layer may result in a portionof the capping unit(s) and/or secondary component diffusing or sinkinginto the wet layer and thereby forming a heterogeneous distribution ofcapping unit(s) and/or secondary component within the thickness of theSOF, such that a linear or nonlinear concentration gradient may beobtained in the resulting SOF obtained after promotion of the change ofthe wet layer to a dry SOF. In embodiments, a capping unit(s) and/orsecondary component may be added to the top surface of a deposited wetlayer, which upon promotion of a change in the wet film, results in anSOF having an heterogeneous distribution of the capping unit(s) and/orsecondary component in the dry SOF. Depending on the density of the wetfilm and the density of the capping unit(s) and/or secondary component,a majority of the capping unit(s) and/or secondary component may end upin the upper half (which is opposite the substrate) of the dry SOF or amajority of the capping unit(s) and/or secondary component may end up inthe lower half (which is adjacent to the substrate) of the dry SOF.

Process Action C: Promoting the Change of Wet Film to the Dry SOF

The term “promoting” refers, for example, to any suitable technique tofacilitate a reaction of the molecular building blocks and/or pre-SOFs,such as a chemical reaction of the functional groups of the buildingblocks and/or pre-SOFs. In the case where a liquid needs to be removedto form the dry film, “promoting” also refers to removal of the liquid.Reaction of the molecular building blocks and/or pre-SOFs and removal ofthe liquid can occur sequentially or concurrently. In certainembodiments, the liquid is also one of the molecular building blocks andis incorporated into the SOF. The term “dry SOF” refers, for example, tosubstantially dry SOFs, for example, to a liquid content less than about5% by weight of the SOF, or to a liquid content less than 2% by weightof the SOF.

In embodiments, the dry SOF or a given region of the dry SOF (such asthe surface to a depth equal to of about 10% of the thickness of the SOFor a depth equal to of about 5% of the thickness of the SOF, the upperquarter of the SOF, or the regions discussed above) has a molar ratio ofcapping units to segments of from about 1:100 to about 1:1, such as fromabout 1:50 to about 1:2, or from about 1:20 to 1:4.

Promoting the wet layer to form a dry SOF may be accomplished by anysuitable technique. Promoting the wet layer to form a dry SOF typicallyinvolves thermal treatment including, for example, oven drying, infraredradiation (IR), and the like with temperatures ranging from 40 to 350°C. and from 60 to 200° C. and from 85 to 160° C. The total heating timecan range from about four seconds to about 24 hours, such as from oneminute to 120 minutes, or from three minutes to 60 minutes.

In embodiments where a secondary component is present, the molecularsize of the secondary component may be selected such that during thepromotion of the wet layer to form a dry SOF the secondary component istrapped within the framework of the SOF such that the trapped secondarycomponent will not leach from the SOF during exposure to a liquid toneror solvent.

IR promotion of the wet layer to the COF film may be achieved using anIR heater module mounted over a belt transport system. Various types ofIR emitters may be used, such as carbon IR emitters or short wave IRemitters (available from Heraerus). Additional exemplary informationregarding carbon ER emitters or short wave IR emitters is summarized inthe following Table (Table 1).

TABLE 1 Information regarding carbon IR emitters or short wave IRemitters Peak Number of Module Power IR lamp Wavelength lamps (kW)Carbon   2.0 micron 2 - twin tube 4.6 Short wave 1.2-1.4 micron 3 - twintube 4.5

Process Action D: Optionally Removing the SOF from the Coating Substrateto Obtain a Free-Standing SOF

In embodiments, a free-standing SOF is desired. Free-standing SOFs maybe obtained when an appropriate low adhesion substrate is used tosupport the deposition of the wet layer. Appropriate substrates thathave low adhesion to the SOF may include, for example, metal foils,metalized polymer substrates, release papers and SOFs, such as SOFsprepared with a surface that has been altered to have a low adhesion ora decreased propensity for adhesion or attachment. Removal of the SOFfrom the supporting substrate may be achieved in a number of ways bysomeone skilled in the art. For example, removal of the SOF from thesubstrate may occur by starting from a corner or edge of the film andoptionally assisted by passing the substrate and SOF over a curvedsurface.

Process Action E: Optionally Processing the Free-Standing SOF into aRoll

Optionally, a free-standing SOF or a SOF supported by a flexiblesubstrate may be processed into a roll. The SOF may be processed into aroll for storage, handling, and a variety of other purposes. Thestarting curvature of the roll is selected such that the SOF is notdistorted or cracked during the rolling process.

Process Action F: Optionally Cutting and Seaming the SOF into a Shape,Such as a Belt

The method for cutting and seaming the SOF is similar to that describedin U.S. Pat. No. 5,455,136 issued on Oct. 3, 1995 (for polymer films),the disclosure of which is herein totally incorporated by reference. AnSOF belt may be fabricated from a single SOF, a multi layer SOF or anSOF sheet cut from a web. Such sheets may be rectangular in shape or anyparticular shape as desired. All sides of the SOF(s) may be of the samelength, or one pair of parallel sides may be longer than the other pairof parallel sides. The SOF(s) may be fabricated into shapes, such as abelt by overlap joining the opposite marginal end regions of the SOFsheet. A seam is typically produced in the overlapping marginal endregions at the point of joining. Joining may be affected by any suitablemeans. Typical joining techniques include, for example, welding(including ultrasonic), gluing, taping, pressure heat fusing and thelike. Methods, such as ultrasonic welding, are desirable general methodsof joining flexible sheets because of their speed, cleanliness (nosolvents) and production of a thin and narrow seam.

Process Action G: Optionally Using a SOF as a Substrate for SubsequentSOF Formation Processes

A SOF may be used as a substrate in the SOF forming process to afford amulti-layered structured organic film. The layers of a multi-layered SOFmay be chemically bound in or in physical contact. Chemically bound,multi-layered SOFs are formed when functional groups present on thesubstrate SOF surface can react with the molecular building blockspresent in the deposited wet layer used to form the second structuredorganic film layer. Multi-layered SOFs in physical contact may notchemically bound to one another.

A SOF substrate may optionally be chemically treated prior to thedeposition of the wet layer to enable or promote chemical attachment ofa second SOF layer to form a multi-layered structured organic film.

Alternatively, a SOF substrate may optionally be chemically treatedprior to the deposition of the wet layer to disable chemical attachmentof a second SOF layer (surface pacification) to form a physical contactmulti-layered SOF.

Other methods, such as lamination of two or more SOFs, may also be usedto prepare physically contacted multi-layered SOFs.

EXAMPLES

A first molecular building block, 1,3,5-triformylbenzene, (TFB,triangular building block) may be reacted with a second molecularbuilding block, 1,4-diamino benzene, (DAB, linear building block) toform a hexagonally networked SOF (FIG. 2). In this case building blockswould be linked by imine (—HC═N—) bonds.

The hexagonal network depicted in FIG. 2 serves as a template formodeling the periodic SOF at the molecular level (FIG. 3) whereintermolecular distances and packing can be ascertained. Because themolecular building blocks are planar molecules and imine bonds are alsoplaner entities a layered structure is predicted from modeling and astructural finger print (X-ray diffraction pattern) can be calculated(FIG. 4).

To understand the electronic properties that can be attained from thisSOF, density functional theory and quantum chemical calculations wereused to generate a density of states diagram (i.e. molecular orbitaldiagram for an extended solid) for the material (FIG. 5). It was foundthat this SOF would possess a Fermi energy level (EF) of −4.5 ev, whichlies within a band (i.e. extended orbital energy level) in the densityof states diagram. In such a case, it is predicted that the materialwould behave essentially as a conductor of electrons.

A computer simulation the product of 1,2,-triformylbenzene reacted with1,4-diamino benzene indicates that a hexagonally networked SOF withthese blocks linked by imine bonds should conduct electrons. Densityfunctional theory and quantum chemical calculations were used togenerate a density of states diagram that predicts a Fermi level of −4.5ev, which lies within a band in the density of states diagram predictingelectron conductivity. Accordingly, such a planer layered structureshould conduct electrons.

It will be appreciated that various of the above-disclosed and otherfeatures and functions, or alternatives thereof, may be desirablycombined into many other different systems or applications. Also,various presently unforeseen or unanticipated alternatives,modifications, variations or improvements therein may be subsequentlymade by those skilled in the art, and are also intended to beencompassed by the following claims.

What is claimed is:
 1. A high mobility structured organic film (SOF)comprising a plurality of segments and a plurality of linkers arrangedas a covalent organic framework (COF), wherein at least a portion of theSOF is periodic, the SOF is a defect-free film having fewer than 10pinholes, pores or gaps greater than about 250 nanometers in diameterper cm², and the SOF possesses a mobility ranging from about 0.1 toabout 3.0 cm²/Vs.
 2. The SOF of claim 1, wherein at least one segment isderived from aryl, arylamine, or thiophene building blocks.
 3. The SOFof claim 2, wherein the at least one segment derived from aryl,arylamine, or thiophene building blocks contains at least one coreselected from the group consisting of triarylamines, hydrazones, andenamines, arene, heteroarene, nitrofluorenones, 9-fluorenylidenes,malonitriles, diphenoquinones, and naphthalenetetracarboxylic diimides,thiophenes, oligothiophenes, fused thiophenes, perylene bisimides,tetrathiofulvalenes, melamine, porphyrin, and phthalocyanine.
 4. The SOFof claim 1, wherein the plurality of linkers are selected from the groupconsisting of covalent bond linkers, ester linkers, ketone linkers,amide linkers, amine linkers, imine linkers, ether linkers, urethanelinkers, and carbonates linkers.
 5. The SOF of claim 1, wherein the highmobility SOF comprises a plurality of mono-segment thick SOFs and theplurality of mono-segment thick SOFs form a layered structure.
 6. TheSOF of claim 1, wherein from about 30% by weight to about 99% by weightof the SOF is periodic.
 7. The SOF of claim 1, wherein the portion ofthe SOF that is periodic is uniformly distributed in the SOF.
 8. The SOFof claim 1, wherein the portion of the SOF that is periodic is notuniformly distributed in the SOF.
 9. The SOF of claim 1, wherein theperiodic portion of the SOF comprises at least one atom of an elementthat is not carbon.
 10. The SOF of claim 1, wherein the SOF is 1 toabout 50 segments thick.
 11. The SOF of claim 1, wherein the pluralityof segments consists of segments having an identical structure and theplurality of linkers consists of linkers having an identical structure.12. The SOF of claim 1, wherein the SOF is a composite SOF.
 13. Anelectronic device comprising the high mobility SOF of claim
 1. 14. Theelectronic device of claim 13, wherein the electronic device is selectedfrom the group consisting of radio frequency identification tags,photoreceptors, organic light emitting diodes, and thin filmtransistors, solar cells.
 15. The electronic device of claim 13, whereinthe electronic device is a electrophotographic imaging member, theelectrophotographic imaging member comprising: a supporting substrate,an electrically conductive ground plane, a charge blocking layer, acharge generating layer, a charge transport layer, an overcoat layer,and a ground strip.
 16. A process for preparing a structured organicfilm (SOF) comprising: (a) performing a computer simulation and/ormaterials modeling to formulate a molecular-level structure of a SOF andbased on a metric of the computer simulation and/or materials modeling;(b) preparing a liquid-containing reaction mixture comprising: asolvent, and a plurality of molecular building blocks each comprising asegment and functional groups, wherein the plurality of molecularbuilding blocks is selected based on results obtained from the computersimulation and/or materials modeling; (c) depositing the reactionmixture as a wet film; and (d) promoting a change of the wet film andforming a dry SOF that substantially replicates the formulatedmolecular-level structure of the SOF; wherein the formulatedmolecular-level structure of a SOF is a high mobility SOF that possessesa mobility ranging from about 0.1 to about 3.0 cm²/Vs, and the SOF is adefect-free film having fewer than 10 pinholes, pores or gaps greaterthan about 250 nanometers in diameter per cm².
 17. The SOF of claim 1,wherein the mobility of the SOF is in the range of from about 0.2 toabout 2.0 cm²/Vs.
 18. The SOF of claim 1, wherein the SOF possess athermal stability higher than 400° C. under atmospheric conditions.